TW517068B - Fiber-reinforced composite and method of making same - Google Patents

Abstract

Fiber-reinforced composites prepared from a depolymerizable and repolymerizable polymer have the processing advantages of a thermoset without being brittle. Impregnation of polymer into the fiber bundle can be achieved with ease, while still producing a composite with excellent physical properties and high damage tolerance.

Description

517068 Zhongli Standard Bureau of the Ministry of Economic Affairs! Printed by the Industrial and Consumer Cooperatives A7 B7 V. Description of the Invention (i) The present invention relates to fiber-reinforced composites. It is known to produce fiber-reinforced composites by stretching dimensional fiber in a drawing device, using resin to impregnate fibers, and simultaneously forming and curing structural parts in a heated mold (refer to the Encyclopedia of Polymer Science and Engineering, Second Edition, Volume 4) John Wiley & Sons, New York, p. 28, 1986). Because effective resin impregnation requires low melt viscosity (a necessary requirement for the acceptable properties of the composite), thermosets are better than thermoplastic materials. Although the thermoset composite has excellent mechanical properties, it has several disadvantages: the elongation of the thermoset matrix is limited, the thermoset precursor is an undesired volatile organic compound or source, the composite cannot be reshaped or recycled, and its production rate Restricted. In recent years, efforts have been made to make composites using thermoplastic materials. For example, U.S. Patent No. 4,439,387 to Hawley teaches extruding crops to melt thermoplastic resin materials through a mold in which fibers are embedded. In U.S. Patent No. 4,559,262, 00§_611, etc., a fiber-reinforced composition is disclosed. The fiber-reinforced composition is obtained by continuously drawing a plurality of fibers through a dipping / shell bath. The dipping bath is sufficiently low in molecular weight (resulting in low solution viscosity). Parts of thermoplastic polymer static melt composition of wet fiber. 〇gaweU Appropriately taught polymers include thermoplastic polyesters, polyamides, polyfluorenes, polyoxymethylenes, polypropylenes, polyarylene sulfides, polyepoxybenzene / polybenzyl Ethylene admixtures' poly_steel and polyetherketones. CogSweu et al. Also teach that in order to achieve acceptable physical properties of the reinforcing composition, a preferred melt viscosity of more than 1 Ns / m2. As such, if the molecular weight of the thermoplastic resin is sufficiently low to achieve a sufficiently low solution viscosity to process the resin, the properties of the resulting surface compound are impaired. The thickness of the single-layer fiber-reinforced sheet (or tape) is limited by the prior art methods. For example, Cogswell et al. Teach that the thickness of a single-layer belt is about 0.01 mm (21 bar, 29 to 31 paper size, China State Standard (CNS) A ^ m ~ (210x797 ^ 1)----! 丨 ——0— r (Please read the notes on the back before filling this page)

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V. Explanation of the invention (3) The consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs of the People's Republic of China printed Ziyue Yue and at least 30% of the volume ratio of the fiber reinforced fiber impregnated with polymer resin extends through $ length, but the fiber length is greater than 100 mm and has a single layer The thickness is at least about 0.2 mm. In a second aspect, the present invention is a method for preparing a fiber-reinforced rigid thermoplastic polyurethane composite. The method includes the steps of continuously stretching a fiber bundle through a melt, and the melt system contains hydrolysis by heating. Stability and heat stability catalyst rigid thermoplastic polyurethane is obtained to a temperature sufficient to depolymerize thermoplastic polyurethane; using depolymerized thermoplastic polyurethane, acid S to immerse and pull Extending the fiber bundle to form a composite melt; forming the composite melt into an object having a thickness of at least 0.2 mm; and then cooling the composite melt to repolymerize the thermoplastic polyurethane, wherein the fibers constitute at least the total volume of the composite 50% by volume. In the second example, the present invention is an improved method for preparing a fiber-reinforced composite by drawing plastic. The method includes the step of impregnating a fiber bundle with a polymer melt. The groove is suitable for the heating duct through which the fiber bundle passes in the transverse direction of the body stream; and the fiber bundle passes through the long groove, so the melt is substantially completely impregnated with the fiber bundle. · The present invention effectively impregnates fiber bundles by providing a thermoplastic having a sufficiently low melt viscosity at elevated temperatures without limiting the molecular weight of the thermoplastic. In a preferred aspect of the present invention, the need for a thermal reservoir for the polymer melt is eliminated by contacting the hot melt flow with the fibers. In this way, unexpected degradation of the polymer is reduced. FIG. 1 is a schematic diagram of a preferred stretcher / extruder device for preparing a fiber-reinforced thermoplastic composite. Figure 2 shows the paper size of the dipping unit and the compaction unit of the drawing machine / extrusion machine. The paper size is in accordance with the state standard of China ((, NS) Λ4 (2) × 297mm) (Please read the back first) (Notes should be filled out again) I #, ιτ • Γ 6 517068 Printed by A7 __________ B7 of the Central Standards Bureau of the Ministry of Economic Affairs, Zhengong Consumer Cooperative V. 5. Description of the invention (4) 'Exploded view. Coincidentally, the figure 3 is an immersion needle Side view. Figure 4 shows the preferred design of the wipe board. The depolymerizable and repolymerizable thermoplastic polymer (DRTp) can be immersed in the fiber bundle by any suitable means, preferably by extrusion methods known in the industry. A fiber-reinforced composite is formed. Preferably, the impregnation method is performed using a combination of fiber drawing and polymer resin melt extrusion according to the method illustrated in Figure 1. It should be understood that this method can be used for any Flowable resin =, not only DRTP impregnated fiber bundles. Now referring to Figure 1, the fiber bundle (10) from the fiber preparation (12) is pulled through the fiber preheating station (14), and contains infrared ceramic heating The fiber bundle (10) can be made by any of many different types Materials include glass, carbon, polyaramide fibers, ceramics, and various metals. The preheating station is hot enough to remove any water present in the fibers, and preheat the fibers to a temperature above the solidification point of the resin melt. Then the fiber bundles (10) Pull through the fiber pre-tensioning unit (16), which is an array of needles to unwind the individual fibers under tension, and then pull through the impregnation unit (18), where the fiber bundle is melted with resin The resin melt is preferably prepared in the following manner. The solid resin is granulated and then dried in a dehumidifier (24) to not more than 200 ppm water, more preferably not more than 100 ppm water. After dehumidification The granular resin is preferably extruded through a heated single-screw extruder (26), which melts the 4 resin by shearing and heating. The resin body is then transferred to the impregnation unit using the heated resin channel (28). (18). Referring now to Figure 2, the impregnation unit (18) contains at least one impregnation needle (20) and a series of rods (22). The impregnation needle (20) includes a generally cylindrical member (30), This paper is suitable for China National Standard Beer (CNS) Λ4 size (2 × 〇297mm) ( (Please read the notes on the back before filling out this page) L0

, 1T Lu! 7 517068 The Ministry of Nucai ’s Intermediate Standards Bureau was negative, τ 消 f co-operative printed A7 B7 V. Description of the invention (5) and contains · a) two longitudinal channels, the first channel is for transferring the resin melt (32), And the two-channel cassette-type heater (34), the heater can maintain the immersion needle (20) to be heated to a temperature higher than the melting point of the resin, or higher than the depolymerization temperature in the case of DRTP, preferably 200. A range of 0 to about 300 ° C; and b) a long groove is formed through the longitudinal opening of the immersion needle (20) which is superposed on the first channel (32) of the bath with the elongated member (36) south. The longitudinal opening at the top of the impregnation needle (20) provides a means for the resin melt to contact the fiber bundle, and the fiber bundle is stretched through the long groove in a lateral direction relative to the resin melt flow through the first channel. The contact between the melt and the fiber bundle is illustrated in Figure 2 (38). It should be understood that "the top opening is only for convenience and is not intended to limit the design of the immersion needle. In addition, the formation of long grooves through which the fiber bundle (10) can pass and contact the resin can be performed in various ways, such as in the longitudinal direction Grind the hollow cylinder. After the fiber bundle (10) is drawn through the long groove of the impregnation needle (20) and wet with the resin melt, the wet fiber bundle (1Ga) is woven through the series wet rod (22) to assist the resin. Impregnation. The impregnated fiber bundle (10a) is drawn through a compaction unit (40), which contains a mold (42) that initially shapes the fiber bundle (ioa) and contains multiple wipes. The removing plate (44) further shapes the fiber bundle (10a) into a desired object and removes excess melt, and then improves the impregnation. Each piece of the erasing plate (44) has an opening with the shape of the part to be formed The opening size and the immersion unit (16) are further reduced downstream until they reach the desired ▲ -shaped cross-sectional size. Figure 4 illustrates the preferred design of the wiper plate (44) by example. • Refer to Figure 1 again Figure, the composite section is pulled through the cooling mold (40, its solid body and lifting Smooth surface. Cooling the mold (46) designed to have a paper size I € _ home towel material ((210X297 ^ 11 ~ ----- (Read Notes on the back and then fill the page)

、 1T I -1 i-· 517068 Α7 Β7 V. Description of the invention (size of the object to be formed. The completed object is preferably pulled by a caterpillar-type towing machine (48)]. The fiber lines that are generally parallel to each other have been completed. The total volume of the fiber-reinforced composite part is at least about 30% by volume, preferably at least about 50% by volume, and more preferably at least about 65% by volume, and the reinforcing fibers generally extend through the entire length of the composite. The stretched plastic section can be cut into any type Required length, from a few millimeters to several kilometers, and further formed, shaped, or joined using techniques well known in the industry, including hot forming, hot stamping, and welding. Surprisingly, the preferred method of the present invention provides The thickness of a single layer is at least 0.2 mm, preferably at least 1 mm, more preferably at least 2¾ meters, and most preferably at least 5 mm. The preferred types of fiber-reinforced composite polymers are depolymerization during heating and re-cooling. Polymerized thermoplastic polymer. Examples of such thermoplastic polymers include polymers with the following structural units: ----------- (Please read the notes on the back before filling this page) Order — Z—C—NH- in the Ministry of Economic Affairs Printed by the Standard Bureau of Zhenggong Consumer Cooperatives where Z is S or 0, preferably 0, and 2 as 3, 0, N • A or cis, preferably 0 or NH, more preferably 0. The preferred DRTp is a thermoplastic polymer Urethanes are thermoplastic polyureas, preferably thermoplastic polyurethanes. DRTP is a unidirectional or bidirectional polymer that can be prepared by the reaction of each of the following suitable chemical calculations: a) diisocyanate or diisocyanate Isothiocyanate, preferably diisocyanate; b) a low molecular weight compound containing two active hydrogen groups (not more than 300 channels) and c) a high molecular weight compound optionally containing two active hydrogen groups (typically molecular weight In the range of about 500 to about 8,000 ear swallows). The combination of low molecular weight compounds of diisocyanate or diisothiocyanate, and the amount of 0 Partially printed standard printed by Zhengong Consumer Cooperative A7 B7 V. Description of the invention (7)% do "hard segment" content 'and high molecular weight compound combination diisocyanate intentionally bite ~ isosulfuric acid Si, composition The so-called "soft segment" content.

I As used herein, the term "active hydrogen group" means a group that can react with isocyanate or isothiocyanate as shown ...

R.-ZH + R-NCZ ——- R.-Z-LnH—R where Z and Z are as defined above, and R and R are linking groups, which can be aliphatic, aromatic or cycloaliphatic or combination. The compound containing two active hydrogens may be a diol, a diamine, a dithiol, an amine, a thiolamine, or a hydroxythiol, and preferably a dithiol. DRTP can be rigid or soft. Soft DRTP preferred thermoplastic polyurethanes (STPUs) are characterized by having a Shore A hardness of not more than 95 or & 25 C. The rigid DRTP is preferably a rigid thermoplastic polyurethane (RTpUs), has a glass transition temperature (Tg) of not more than 50 ° C, and typically has a hard segment content of at least 75 / 〇. The disclosure and preparation of RTPUs are described, for example, by Goidwasser et al. In U.S. Patent 4,376,834. RTPUs are compounds of the present invention, preferably thermoplastic polymers. Examples of commercially available RTPIJs include thermoplastic polyurethanes for the ISOPLASTi process (trade name of The Dow Chemical Company). Preferred diisocyanates include aromatic, aliphatic, and cycloaliphatic diisocyanates, and combinations thereof. Representative examples of preferred diisocyanates are referenced in U.S. Patents 4'3 85,133,4,522,975; and 5,167,899. Preferred diisocyanates include 4,4'-diisocyanatodiphenylmethane, p-phenylene diisocyanate, I, 3 '(isocyanatomethyl) cyclohexane, i, 4_ Diisocyanate cyclohexane, /, methylene monoisocyanate, naphthyl diisocyanate, 3,3, _dimethyl (Please read the precautions on the back before filling this page) Order 10 517068 Printed by Standard Bureau of Zhenggong Consumer Cooperatives A7 B7 V. Description of the invention (8) 4-4,4'-biphenyl diisocyanate, 4,4, -diisocyanate dicyclohexylmethane, and 2,4-methylene Stupid diisocyanate. More preferred are 4,4, diisocyanatodicyclohexylfluorane and 4,4, diisocyanatodiphenylmethane. The most preferred is 4,4, _diisocyanate. Preferred low-molecular-weight compounds containing two active hydrogen groups are ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, hexylene glycol, diethylene glycol, Triethylene glycol, tripropylene glycol, tetraethylene glycol, neopentyl glycol, ^ 4-cyclohexanediol, 1,4-cyclohexanedimethanol, // hydroxyethyl) hydroquinone, 2,2_ Samarium (β-hydroxy-4-ethoxyphenyl) propane (ie, ethoxylated bisphenol A) and mixtures thereof. Preferred chain extenders are M-butanediol, 156-hexanediol, M_cyclohexanediethanol, diethylene glycol, triethylene glycol, tripropylene glycol, and mixtures thereof. DRTP may optionally contain a structural unit formed of a high molecular weight compound containing two active hydrogen groups, preferably having a molecular weight of preferably not less than about 750 ′, more preferably not less than about 1,000, and most preferably Diols below about 15,000; and preferably no higher than about 6000, and more preferably no higher than about 5,000. The units of high molecular weight diols are low enough for DRTP's better RTPU, so the Tg of DRTP is 50 ° C. Preferably, the high molecular weight diol unit is no more than about 25 'of the RTPU, more preferably no more than about 丨 0, and most preferably no more than about 5% by weight, to about 0% by weight RTPU. It is preferably a polyester diol or a polyether diol or a combination thereof. Examples of preferred polyglycol glycols and polyether glycols include polylactone glycol, polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyethylene glycol Adipate, polybutylene adipate diol, polyethylene adipate and poly (hexamethylene carbonate diol), or a combination thereof Du Suchuan China National Standard ((, NS) M specifications (21 × 297 mm) (Please read the precautions on the back before filling in this page)

1T 11 517068 Printed by A7 B7, Male Workers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (9) 〇 The isocyanate pair XH of the present application should preferably be 〇H ratio from about 0.95: 1, better 0.975: 1, and more preferably from about 0.8985: 1 to about 105: 1, more preferably about 1.025: 1, and more preferably about 1.015: 1. DRTP, preferably RTPU, can be prepared excellently in the presence of an effective amount of hydrolytic and thermal stability catalysts, which can catalyze the reaction between an isocyanate group and an active hydrogen group. The active hydrogen group is preferably a hydroxyl group, which forms Urethane, urea, or thiogland linkages, preferably urethane linkages, which remain active during polymer depolymerization and catalyze the re-bonding between the urethane, urea, or thiourea Formation, preferably re-formation of the amino acetic acid bond and re-establishing molecular weight. Examples of such catalysts are Sn + 2 such as stannous octoate; and sn + 4 catalysts such as dialkyltin dithiolates, preferably dimethyltin dithiolates (available in FOMREZ UL-22, a product of Witco Chemical Company) (Namely obtained), and dialkyltin dicarboxylate, as disclosed in detail in U.S. Patent 3,661,887. More preferably, the catalyst is present in an amount of from about 0.000 to about 5 weight 0 / 〇. Non-DRTP thermoplastic resin can be used in combination with DRTP to make the composite of the present invention, but the amount of non-DRTP is low enough so that the melt viscosity of the resin is kept low enough to effectively impregnate the fiber bundles. Examples of non-DRTP include acrylonitrile-butadiene · ethylene copolymers, polystyrenes, polyphenylene oxides, polystyrene oxide polystyrene compounds, polyoxymethylene groups, polypropylene Dilute, polyamines, polybutylene terephthalate, poly (butylene terephthalate), poly (butylene terephthalate) and poly (ethylene terephthalate) Ester copolymers, styrene-ethylene-acetonitrile copolymers, and ethene-propylene-diene terpolymers. The compound also includes additives such as flame retardants, UV stabilizers, and pigments. This paper is described in the state Chinese National Standard (CNS) Λ4 specification (210X 297 mm) (Please read the precautions on the back before filling this page)

、 1T f 12 517068 A7 '------- B7 V. The day of invention ^ ~, dyes, antistatic agents, antimicrobial agents, fungicides, mold removers and flow promoters. \ (Please read the precautions on the back before filling this page) Reinforced thermoplastic composites can be prepared by DRTP, which has unexpectedly superior physical properties compared to composites made from non-decomposable polymerized and repolymerized thermoplastics. Additionally, The use of drtp, especially the preferred device, requires a fast pull rate, preferably at least about 1 m / min, more preferably at least about 2 m / min, more preferably at least about 5 m / min, and most preferably at least about 10 m Per minute without sacrificing the degree of impregnation. Preferably, the composite has a flexural strength of at least 500 Mpa, more preferably at least 750 MPa, and most preferably at least 200 MPa, even when glass fibers are used. Much higher strength can be achieved using polyaramide and carbon fibers. The reinforced composites of the present invention can be used in a wide variety of applications that require extremely high strength and rigidity, as well as extra sensitivity, such as snow shows, ski poles, parasols, tent posts, concrete, anti-collision barriers, doors or Window frames, cables and fiber optic cables. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention. An example printed by the China Industrial Standards Bureau of the Ministry of Economic Affairs and a cooperative—the impregnation with rigid thermoplastic polyurethane · glass fiber made of 24 bundles of fibers (Owen Corning Corporation, R43S, 2400 Te) 3 layers, pulled through 240 ° C preheating station. ISOPAST 2530 Polyurethane G thermoplastic resin (Dow Chemical Co., Ltd.) has been preheated in a Pirwin desiccant dryer at 95 ° C for more than 8 hours and processed on a Colin 4 single screw extruder (Screw speed 25 rpm, barrel temperature 250 ° C (hopper), 260 ° C, and 270 ° C). The connecting rod is set at 280 ° C. Each layer of fiber is pulled through the impregnation needle, where the fiber is saturated with polyurethane melt and then passes through a number of thermal books Λ ㊈ ㊈ J1] China National Standard Pool (CNS) (21〇X 297 ^ f) ~ -13 -517068 A7 -________ Β7 V. Description of the invention (u) Talent weaving. The dimensions of the respective long grooves of the impregnated needle are 0.8 mm in height and 60 mm in width. The length of the first groove is 120 mm and the diameter of the groove is 30 mm. The immersion needle was maintained at 285 ° C, and the other rods were maintained at 260 ° C. The fiber draw rate was 2 meters / minute. Production of strips measuring 2 cm wide x 2 mm thick (and variable length). The fiber-reinforced composite has a flexural strength of 1300 MPa and a flexural modulus of 41 GPa (tested by BS 2787). Comparison of component numbers 40. Fiber bundles 30. Cylindrical pieces 12 ... Fiber preparation 32 ... First channel 14 ... Fiber preheating station 3 4 ... Second channel 16 ... Fiber pretensioning unit 3 6 · · · Slim pieces 1 8… immersion unit 3 8… contact 2… immersion needle 40… compaction unit 22… rod 42… mold 24… dehumidifier 44… wipe plate 26… single Screw extruder 46 ... Cooling mold 28 ... Channel 48 ... Caterpillar towing machine (Please read the precautions on the back before filling this page)

、 1T .1 Printed by Wu Gong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs This paper size applies to China's national standard ((, milk) / \ 4 size (210 '/ 297 mm) 14

Claims (1)

517068 Patent No. 87110640 Patent Application Amendment to Patent Scope Amendment Date: December 1990 1. A fiber-reinforced thermoplastic composite containing a depolymerizable and repolymerizable thermoplastic polymer resin, and at least 30% The% volume ratio reinforced fiber is impregnated with a polymer resin and extends through the entire length of the composite, but the length of the composite is more than 100 m, and has a single layer thickness of at least 0.2 mm, wherein the thermoplastic polymer resin contains Structural units of the following formula: —Z—C—NH— where Z is S or 0; and Z 'is S, 0 or NH. 2. The thermoplastic composite according to item 1 of the Shenyan patent, wherein z and z are 0 and wherein the composite has a single-layer thickness of at least about 0.5 mm. 3. The thermoplastic composite of claim 1 or 2, wherein the thermoplastic polymer resin is a thermoplastic polyurethane having a Tg of at least 50 ° C. 4. The thermoplastic composite of claim 3, wherein the fiber is at least 50% by volume of the resin, and the composite has a thickness of at least 1 mm. 5. A method for preparing a fiber-reinforced rigid thermoplastic polyurethane composite object, the method comprising the following steps: a) continuously stretching a fiber bundle through a melt, the melt system comprising hydrolysis- and heat-stability through heating The rigid potential of the catalyst is obtained at a temperature sufficient to depolymerize the thermoplastic polyurethane; b) using the depolymerized thermoplastic polyurethane to impregnate the stretched paper Lai China National Group (CNS) Eighty-fourth Secret (21QX297 Gongchu) 15 517068 ABCD VI. Patent application fiber bundles to form a composite melt; C) Forming the composite melt into objects with a thickness of at least 0.2 mm And d) cooling the melt of the composite to repolymerize the thermoplastic polyamine 'based formic acid; wherein the fiber system accounts for at least 50% by volume of the total volume of the composite. Installation-6. The method according to item 5 of the scope of patent application, wherein in step (b), the fiber is impregnated by overheating a polyaminoacetate tube, the tube having a direction substantially transverse to the resin flow direction. Long longitudinal grooves are suitable for fiber bundles to pass through; and fiber bundles are passed through long grooves, so the resin impregnates the fiber bundles. Order 7 · —An improved method for preparing a fiber-reinforced composite by drawing plastic, the method includes the step of impregnating a fiber bundle with a polymer melt, and the improvement part includes flowing the melt through a heating duct, the duct having suitable fibers The bundles pass through the long grooves in the longitudinal direction of the melt in the transverse direction; and the fiber bundles are passed through the long grooves, so the melt is substantially completely impregnated with the fiber bundles. Line 8. The method according to item 7 of the scope of patent application, wherein the catheter having a generally narrative long slot includes an elongated member mounted over an elongated and generally cylindrical receptacle. 9. The method of claim 7 or 8, wherein the polymer is thermoplastic. 10. The method of claim 7 or 8, wherein the polymer is a thermosetting polymer. 11. The method of claim 9 in which the thermoplastic polymer has a thermoplastic polyurethane having a Tg of at least 50 ° C. 12. The method of claim 7 or 8, wherein the polymer melt further comprises a non-decomposable and repolymerizable polymer. 16